Alkyl halo-diphenyloxides



Patented Aug. 29, 1939 UNITE STATES- arzosas Anna. mo-mrnmrnoxmas Gerald B. Coleman and'Robert n. Drcisbach,

Midland, 'Mich., asaignors to The Dow Ghemi- 1 ca! Company, Midland, Mich, a corporation of No Drawing. Applies on March 29, 1937,

Serial N0. 33,645

9 Claims. (01. 260- 812).

The present invention concerns certain new alkylated halo-diphenyloxidesand mixtures thereof, as well as amethod of making the same. The alkyl-halo-dipehnyloxide products .herein disclosed varyfrom oily iiquidsto resinous solids at room temperature; They comprise new compounds which contain at least one alkyl radical having two or more carbon atomsand at least one nuclear halogen atom per molecule. The 10 products are particularly valuable as dielectric agents in condensers, transformers, and other electric equipment, being less flammable and more fluid than many other such dielectrics; they may also begemployed as plasticizers in resins, varnishes, etc.

1 The products are prepared by successively halogenating and alkylating diphenyloxide as hereinafter described. Said'reactions may be carried out in any desired order, i.-e., the diphenyloxide may'be first halogenated and then alkylated, or first alkylated and thenhalogenated. Theinvention, then, consists in the new prod nets and methods hereinafter fully described and particularly pointed out in the claims, the following description setting forth but several of the ways in which the vention may be employed.

In preparing an alkylated halo-diphenyloxide, diphenyloxide is preferably first halogenated, e. g., by'reaction with chlorine or bromine as described in U. S. Patent 2,022,634, to obtain a halo-diphenyloxide containing from one to six halogen atoms per molecule. The halo-diphenyloxide is then treated with a small -proportion, e. g., between 0.01 and 0.05 molecular equivalent of aluminum chloride, after which an alkyl halide or an olefine is gradually introduced while maintaining the mixture at a reaction temperature. Examples of such alkyl halides and olefines 40 arez-methyl chloride, ethyl chloride, ethyl bromide, normal propyl bromide, isopropyl chloride, normal butyl chloride,- isobutyl chloride, ethylene, propylene, normal butylene, isobutylene, etc. The temperature required for the reaction varies somewhat with the alkyl halide or olefine employed, the kind and proportion of catalyst used in the reaction, and the extent of alkylation desired. However, the reaction usually occurs smoothly at temperatures between 125 and 175 C., but may sometimes be carried out at lower or higher temperatures, e. g., about 50 or 225 C.

When the reaction is completed the mixture is cooled, washed with aqueous hydrochloric acid to remove the catalyst, neutralized with an aqueprinciple of the inous alkali, dried, and heated to vaporize therefrom any unreacted alkylhalide or oleflne. The residual product is usually a liquid mixture of alkylated halo-diphenyloxides comprising .150- meric compounds and non-uniformly alkylated 5 compounds containing varying numbers of'alkyl' substituents. If desired, individual .alkyl-halodiphenyloxides may be separated from such mixtures by distillation or" otherwise, but thermixtures themselves possess- .properties rendering o them well suited to -use for industrial purposes, e. g., as dielectric agents y By reacting a halo-diphenyloxidesimultaneo ly or successively withwtwo" or .more alkyl halides or olefines in the manner iust described, an 15 alkylated halo-diphenyloxlde containing two'or more different alkyl radicals, e.- g., methyl-ethylbrom-diphenvloxide, ethyl-isopropyl dichlor-diphenyloxide, etc; may beproducedi" Likewise," useful mixtures may be produced byallrylating a mixture of two or more halo-diphenyloxldes in the above-disclosed manner.

Our new alkyl halo-diphenyloxlde products may also be prepared by first alkylating diphenyloxide in accordance with procedure similar to thatdescribed above and thereafter halogenating the alkylated diphenyloxide, preferably. at elevated temperatures in the presence of a nuclear halogenation catalyst, such as 'iron chloride. The reaction temperature required for the halogenation depends somewhat upon the halogen employed in such reaction. When bromine. is used the halogenation proceeds satisfactorily at temperatures above 0., whereas the reaction with chlorine occurs most smoothly at temperatures above 121 0 7 Alter completingthmhal: ogenation the reaction mixture is cooled, neutralized, and dried. The dried product is usually a mixture of isomeric and other closely related, e. g. homologous, alkyl-halo-diphenyloxides. ,It may be used without further treatment for dielectric purposes, etc. If desired, it may be separated by distillation or otherwise into its components, which may be used as dielectric agents, as intermediates from which 45 other products may be prepared, and so forth.

The following examples illustrate a number of ways in which the. principle of our invention has been employed, but are not to be construed as limiting the invention: 50

Example I A mixture of 0.2 grain-mol of aluminum chloride (AlCh) and 9.0 gram-moles (1822 grams) of crude monochlor-diphenyloxide, (havin a 55 boiling point of about 125 to 145' c. at 2.5 to

5 millimeters absolute pressure. a specific :ravity of about 1.20, and a chlorine content of 16.6 per cent by weight) was heated toand main- "tained at a temperature of 150 (2., while 8.0

B.r.no 5 Refractive M geasome. index Mono-ethyl chlordiphcnylwearer ues m num liii'ltF-iiii'e'iyiiidi m-ma- Loon 1.1m Amixturcoi ethyidsloo dipheuyl 2J0t0210 1.01s um Therespec ve oi the compoundsseparated,

based on the chloro-diphenyloxlde reacted. were:-

. mono-ethyl chlor-diphenylo'xide 82.4%.- di-ethyl chlor-diphenyloxide 6.7%, diphenyloxide 6.5%.

same and poly-ethyl chlor- 421 moles .(470 my ethyl (having 8. boiling P011115 01 13".00 163.O- 8t 10 mm. pressure End a speciflcf gravity. oi. 1.02 20/4- O.) was heated'.to and maintained at. a temperature or 160 to 1'10 C. in

while 8.8 moles of, gaseous chlorine was during 8.5 hours. product was washed with hot solution and dried. The driedproductwasrdistiiledr under reduced whereby. .162 or to1700.at4mm.pr'essureand883grams oiablackresidualresinwereobtained. Theoil was redistilled, whereby the following -fractions wereseparated:

Compositionoitmetlon Boilingpoint M A mixture oi-cth l mcnochlob andethyldidlloriphen losidol. M186 OJSrnm. 2.0 Ethyl tridilor-diphenyloxizlah..- 105% 5 mm. to 84.2 rm. 0:75:11 rid-sema- '180to210lat s'mm. is: ad flpeflta-chlor-diphanyl- '1heresiniromtheinltialdistillationhadasott-- ening point 01 about 50 0.. a chlorine content of 30.9 percent. and an electrical breakdown potential of 16,000 volts per 0.1 inch.

7 Example 3 To a mixture of 0.2 gram-moi of anhydrous aluminum chloride and 10.0 gram moles oi chlordiphenyloxide (of the same quality as in Example 1) maintained at a temperature of C. was added to 8.77 moles of gaseous propyiene'during 6.5 hours. The reaction mixture was washed and dried as in Example 1, whereby 2388 grams 0! a light oil boiling chiefly over the range 115 to 200 C. at 6 mm. pressure was obtained. This oil was then iractionaliy distilled at reduced pressure, whereby the following compounds were separated:

. RM" P p -20l40., indwig hcnyi ma D isopropyl chior-diphenyloxida.

Mono-loo The respective yields 01 thecompounds separated, based on the chlor-diphenyloidde used.

were: 'mono-isopropyl -ch10r-diphenyloxide 453%; di-isopropyl chlor-diphenyloxide 14.2%.

' Example 4 A mixture of 0.2 gram-moi of anhydrous aluminum chloride and 9.0 moles of chlor-diphenyloxide (oi the. same quality as in Example 1) was heated to and maintained at a temperature of 85-95 C.-whlle 9.0 moles of tertiary butyl chloride was added during 3.5 hours. The reaction mixture was washed and dried as in Example 1,

whereby 2218 grams of a light oil was obtained. I

This material wasthen fractionally distilled at reduced pressure, whereby, the following compounds were separated:

v B. P. at 0 Refractive save 0. index 113 Maximum-w butyl chlcrdiphcny do 173 to 176 1.088 1. 6611 Di-tertisry butyl chlor-diphonyloxido 192 to 105 l. 0547 l. 5501 Anisomeric di-tertiary bntyl chlor-dlpbonyl-oxide-.-.-.-- 198 to fill l. 0306 1. 5470 The yields 01 the respective compounds based on the chlor-diphenyloxide consumed were: mono- -tertiarybutyl chlor-diphenyloxide 52.4%, total chlor-diphenyloxides 15137..

"Example 5 To a mixture of 0.2 gram-moi oi. anhydrous aluminum chloride and 4.5 moles oi dichloro-dlphenyloxlde (having a' boiling point of 166 to 175" C. at 8 mm. pressure, a specific gravity of 1.304 20l4 0.. a refractive index of 1.5992 at 20 6.. and a chlorine content of 30.5 per cent by weight) maintained at a temperature of 90 to (ii-tertiary butyl 95 C., was added 4.61 moles 01 sec. butyl chloride during 0.83 hour. The reaction product 'was washed with concentrated hydrochloric acid, then withsodium carbonate solution and was finally dried over calcium chloride; 1158 grams of an oil boiling over the range C./8 mm. to 208 0/5 mm. was obtained. This oil was fractionally distilled at reduced pressure, whereby the following compounds were separated:

B. P. at 5 mm. pressure. C.

Refractive Sp. gr. at 20l24 0. index a?) Compound Mono-sec. butyl dichiorodiphenyloxide 1. 2014 Di-sec. bntyl dichlor-diphenyloxide.

The yields of the respective compounds based on the dichlordiphenyloxide consumed were: mono-secondary butyl diphenyloxide 48.2%; di-

. secondary butyl diphenyloxide, 18.5%.

Example 6 To a mixture 02 0.2 gram-mo. oi anhydrous 19 hours.

aluminum chloride and 9.39 moles of liquid tetrachlor-diphenyloxide, (having a specific gravity of 1.487 20/4 C., a refractive index of 1.6164 at 20 C., and a chlbrine content of 47 .0 per cent by Weight) maintained at a temperature of about C. was added 5.02 mols of propylene during The reaction product was washed and dried as in Example 5, whereby 2960 grams of an oil boiling over the range 95207 C. at 2 mm. pressure were obtained. A portion of this oil was fractionally distilled at reduced pressure, whereby thefollowing compounds were separated:

The products obtained in each of the foregoing examples possessed electrical characteristics, i. e., low dielectric constant, low power factor, high electrical resistance and high break-down potential rendering them well adapted for use as dielectric agents. I

Other modes of applying the principle of our invention may be employed instead of those explained,- change being made as regards the details herein disclosed, provided that the products or method stated by any of the following claims or the equivalent of such stated products or method be employed.

We, therefore, particularly point out and distinctly claim as our invention:

1. A lower alkyl-halo-diphenyloxide containing at least one lower alkyl radical having at least two carbon atoms.

2. A mixture of lower alkyl-halo-diphenyloxides each containing at least one lower alkyl radical having at least two carbon atoms.

3. A liquid non-uniformly alkylated chlor-diphenyloxide mixture comprising ethyland polyethyl chlordiphenyloxides as major ingredients.

4. A liquid non-uniformly alkylated chlor-diphenyloxide mixture comprising isopropyl and poly-isopropyl chlor-diphenyloxides as major ingredients.

5. Monoethyl mono-chlor-diphenyloxide, having a boiling point of to 164 C. at 6 millimeters absolute pressure, a specific gravity of 1.168 20/4 C., and a refractive index 1213 of 1.707.

6. Diethyl mono-chlor-diphenyloxide, having a boiling point of to 174 C. at 6 millimeters absolute pressure, a specific gravity of 1.094 20/4 C., and a refractive index 1m of 1.706.

7. Mono-isopropyl mono-chlor diphenyloxide, having a boiling point of 156 to 169 C. at 6 millimeters absolute pressure, a specific gravity of 1.126 20/4 C., and a refractive index 11.1) 1.567.

8. The method which comprises reacting a halo-diphenyloxide with at least one compound selected from the class consisting of lower alkyl halides and lower olefines in the presence of a Friedel-Crafts catalyst.

9. The method which comprises reacting a chlor-diphenyloxide with at least one compound selected from the class consisting of lower alkyl halides and lower olefines in the presence of a Friedel-Crafts catalyst.

GERALD H. COLEMAN. ROBERT R. DREISIBACI-I 

